CN105414795B - A kind of low temperature resistant oxidation resistant lead-free scolding tin and preparation method thereof - Google Patents
A kind of low temperature resistant oxidation resistant lead-free scolding tin and preparation method thereof Download PDFInfo
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- CN105414795B CN105414795B CN201511028096.3A CN201511028096A CN105414795B CN 105414795 B CN105414795 B CN 105414795B CN 201511028096 A CN201511028096 A CN 201511028096A CN 105414795 B CN105414795 B CN 105414795B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/40—Making wire or rods for soldering or welding
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
Abstract
The invention provides a kind of low temperature resistant oxidation resistant lead-free scolding tin and preparation method thereof.The present invention carries out oxidation carbon removal treatment to original tin material；On the basis of Pb-free solder basic element composition, addition can suppress the elemental composition gone bad under tin (Sn) element oxide and low temperature, form anti-oxidant and low temperature resistant scolding tin basal body structure；Butt welding tin matrix is melted to high temperature fused state, and then rapid condensation processing again under inertia protection atmosphere；And the further rotten surface membranization processing of pre- anti-oxidation, growth filament and tin element is implemented on butt welding tin matrix surface, while keeping the welding performance of scolding tin after film forming.The present invention is relatively effective to solve that Pb-free solder is oxidizable, easily growth filament, the new problem such as easy disintegrating under low temperature.
Description
Technical field
The present invention relates to alloy conductive field of material technology, more particularly to a kind of low temperature resistant oxidation resistant lead-free scolding tin and its system
Preparation Method.
Background technology
Common scolding tin is the conductive solder material using tin-lead (Sn-Pb) alloy as main component, and wherein lead content exists
37wt% (percentage by weight) left and right.It is also larger to air and soil pollution because lead is poisonous to human body, therefore with Pb-free solder
The inevitable direction that common scolding tin has become the development of welding material technology is substituted, in developed country even in the way of legislation
It is distinctly claimed and applies Pb-free solder.
Pb-free solder adds copper (Cu) element formation Sn-Cu alloys, wherein Cu members using tin (Sn) as main component
Cellulose content is 0.7wt%；And add silver-colored (Ag) element formation Sn-Ag alloys, wherein Ag constituent contents 3wt%；Or addition
Copper (Cu) and silver-colored (Ag) element formation Sn-Ag-Cu alloys, wherein Ag constituent contents 3-3.5wt%, Cu constituent contents 0.5-
0.75wt%；Above alloy is respectively provided with eutectic morphology.
Compared with leaded common scolding tin, although Pb-free solder in terms of environment protection health be improved significantly, at it
There are still deficiency in application, its subject matter includes：Because Theil indices increase causes inoxidizability to be deteriorated, scolding tin surface hair
It is black, influence tin liquor mobility in oxidizing slag, thus welding process can be largely produced in fusing, is easily adhered to, air bubble is produced.
Moreover, resistance to low temperature is decreased obviously, thin filiform is grown on surface using meeting in subzero less than 30 degree of temperature
Phenomenon, this be due to scolding tin surface oxide layer due under low temperature Volume Changes occur crack, in the case where there is crack,
On the one hand tin is pressurized and is grown to elongate, threadlike under the stress expanded with heat and contract with cold, on the other hand with the aging of scolding tin, Sn-
Cu alloys constantly attack top layer from inside to outside, so as to produce filament from crack；These filaments easily bring short circuit etc. to destroy；And
Tin is substantially accelerated in the speed of subzero less than 30 degrees Celsius its rotten powdereds, and the tin material for even resulting in welding position collapses completely
It is bad；Common scolding tin can suppress to grow the effect of filament and powdered due to lead element contained therein, thus can be low
Temperature is lower to be applicable, on the contrary, Pb-free solder is then difficult in high latitude areas such as China northeast and faces subzero 30 degrees Celsius of low temperature
Applied under particular surroundings.
The content of the invention
In order to overcome the defect that above-mentioned prior art is present, the present invention is intended to provide a kind of low temperature resistant oxidation resistant lead-free scolding tin
And preparation method thereof.The present invention carries out oxidation carbon removal treatment to original tin material, by further reducing carbon impurity content, suppression
Sn-Cu alloy growths in scolding tin processed；On the basis of Pb-free solder basic element composition, addition can suppress tin (Sn) elemental oxygen
The elemental composition gone bad under change and low temperature, forms anti-oxidant and low temperature resistant scolding tin basal body structure；It is right under inertia protection atmosphere
Scolding tin matrix melts to high temperature fused state, and then rapid condensation processing again, strengthens resistant to deterioration performance；And butt welding tinbase body surface
The further rotten surface membranization processing of pre- anti-oxidation, growth filament and tin element is implemented in face, while keeping scolding tin after film forming
Welding performance.
Low temperature resistant oxidation resistant lead-free scolding tin of the present invention, including scolding tin matrix and superficial film, wherein, scolding tin matrix
Composition by weight percent is：
Tin (Sn) 97.95-98wt%, silver (Ag) 0.28-0.32wt%, copper (Cu) 0.72-0.68wt%, gallium (Ga) 0.1-
0.2wt%, indium (In) 0.05-0.1wt%, rhenium (Re) 0.7-0.85wt%, carbon (C) are less than or equal to 0.05wt%；
Also, the scolding tin matrix is in an inert atmosphere by molten condition with the speed of 10-15 degrees Celsius of cooling per second
What solidification was formed；
Scolding tin matrix surface has the superficial film grown according to procedure below：First, following composition and concentration are configured
Solution：SnSO220-30g/L, 1- hydroxyethyl -2,2- bis- substituted phosphate 40-60g/L, sodium hypophosphite 40-120g/L, to benzene
Diphenol 5-8g/L, regulation pH value is to be basic in neutrality, and temperature is heated to 40-60 degrees Celsius；Scolding tin matrix immersion is described
Solution 1-1.5 hours, to grow the superficial film in scolding tin matrix surface.
Preferably, the composition by weight percent of scolding tin matrix is：Tin (Sn) 97.95-98wt%, silver (Ag) 0.3wt%,
Copper (Cu) 0.7wt%, gallium (Ga) 0.15wt%, indium (In) 0.05wt%, rhenium (Re) 0.8wt%, carbon (C) is less than or equal to
0.05wt%.
Or, the present invention provides a kind of low temperature resistant oxidation resistant lead-free scolding tin, including scolding tin matrix and superficial film, wherein,
The composition by weight percent of scolding tin matrix is：
Tin (Sn) 97.95-98wt%, silver (Ag) 0.28-0.32wt%, copper (Cu) 0.72-0.68wt%, gallium (Ga) 0.1-
0.2wt%, indium (In) 0.05-0.1wt%, cerium (Ce) 0.7-0.85wt%, carbon (C) are less than or equal to 0.05wt%；
Also, the scolding tin matrix is in an inert atmosphere by molten condition with the speed of 10-15 degrees Celsius of cooling per second
What solidification was formed；
Scolding tin matrix surface has the superficial film grown according to procedure below：First, following composition and concentration are configured
Solution：SnSO430-45g/L, 1- hydroxyethyl -2,2- bis- substituted phosphate 40-60g/L, sodium hypophosphite 40-120g/L, Ce
(SO4)25-8g/L, regulation pH value is to be basic in neutrality, and temperature is heated to 40-60 degrees Celsius；The scolding tin matrix is immersed into institute
Solution is stated 1-1.5 hours, to grow the superficial film in scolding tin matrix surface.
Preferably, the composition by weight percent of scolding tin matrix is：Tin (Sn) 97.95-98wt%, silver (Ag) 0.3wt%,
Copper (Cu) 0.7wt%, gallium (Ga) 0.15wt%, indium (In) 0.05wt%, cerium (Ce) 0.8wt%, carbon (C) is less than or equal to
0.05wt%.
Preferably, the pH value is adjusted to 6.5-7.5.
Preferably, the growth thickness of the superficial film is 7-15 microns.
The invention provides a kind of preparation method of low temperature resistant oxidation resistant lead-free scolding tin, it is characterised in that including following step
Suddenly：
Step 1, the metallic tin (Sn) for taking phosphorus content to be not higher than 0.4wt% is raw material, and metallic tin (Sn) is melted into 350-
After 360 degrees Celsius, insulated and stirred 20-30 minutes；Pure oxygen, oxidation removal carbon therein (C) are blown into the tin (Sn) of molten condition
Element；
Step 2, silver-colored (Ag), copper (Cu), indium (In), rhenium (Re) are added to the metallic tin (Sn) of the molten condition after oxidation,
And continue stirring 10-20 minutes；It is continuously heating to after 420-430 degrees Celsius, addition gallium (Ga) simultaneously continues stirring 10-20 minutes,
Being cooled to sizing below fusing point turns into scolding tin matrix；Wherein, the percentage by weight of each composition is added during formation scolding tin matrix
For：
Tin (Sn) 97.95-98wt%, silver (Ag) 0.28-0.32wt%, copper (Cu) 0.72-0.68wt%, gallium (Ga) 0.1-
0.2wt%, indium (In) 0.05-0.1wt%, rhenium (Re) 0.7-0.85wt%, carbon (C) are less than or equal to 0.05wt%；
Step 3, more than 160 degrees Celsius are warming up to again under the inert atmosphere full of argon gas to the scolding tin matrix, so
The scolding tin matrix is warming up to the speed of 95-100 degree per seconds Celsius again to melt, keep after 3-5 minutes molten conditions afterwards,
Inert atmosphere full of argon gas is solidified as scolding tin matrix again by molten condition with the speed of 10-15 degrees Celsius of cooling per second；
Step 4, following composition and the solution of concentration are configured：SnSO220-30g/L, 1- hydroxyethyl -2,2- bis- generations phosphoric acid
Ester 40-60g/L, sodium hypophosphite 40-120g/L, hydroquinones 5-8g/L, regulation pH value is to be basic in neutrality, and temperature is heated to
40-60 degrees Celsius；The scolding tin matrix is immersed described solution 1-1.5 hours, to grow the table in scolding tin matrix surface
Face mask layer.
Preferably, formed during scolding tin matrix and add the percentage by weight of each composition and be：Tin (Sn) 97.95-
98wt%, silver (Ag) 0.3wt%, copper (Cu) 0.7wt%, gallium (Ga) 0.15wt%, indium (In) 0.05wt%, rhenium (Re)
0.8wt%, carbon (C) is less than or equal to 0.05wt%.
The invention provides a kind of preparation method of low temperature resistant oxidation resistant lead-free scolding tin, it is characterised in that including following step
Suddenly：
Step 1, the metallic tin (Sn) for taking phosphorus content to be not higher than 0.4wt% is raw material, and metallic tin (Sn) is melted into 350-
After 360 degrees Celsius, insulated and stirred 20-30 minutes；Pure oxygen, oxidation removal carbon therein (C) are blown into the tin (Sn) of molten condition
Element；
Step 2, silver-colored (Ag), copper (Cu), indium (In), cerium (Ce) are added to the metallic tin (Sn) of the molten condition after oxidation,
And continue stirring 10-20 minutes；It is continuously heating to after 420-430 degrees Celsius, addition gallium (Ga) simultaneously continues stirring 10-20 minutes,
Being cooled to sizing below fusing point turns into scolding tin matrix；Wherein, the percentage by weight of each composition is added during formation scolding tin matrix
For：
Tin (Sn) 97.95-98wt%, silver (Ag) 0.28-0.32wt%, copper (Cu) 0.72-0.68wt%, gallium (Ga) 0.1-
0.2wt%, indium (In) 0.05-0.1wt%, cerium (Ce) 0.7-0.85wt%, carbon (C) are less than or equal to 0.05wt%；
Step 3, more than 160 degrees Celsius are warming up to again under the inert atmosphere full of argon gas to the scolding tin matrix, so
The scolding tin matrix is warming up to the speed of 95-100 degree per seconds Celsius again to melt, keep after 3-5 minutes molten conditions afterwards,
Inert atmosphere full of argon gas is solidified as scolding tin matrix again by molten condition with the speed of 10-15 degrees Celsius of cooling per second；
Step 4, following composition and the solution of concentration are configured：SnSO430-45g/L, 1- hydroxyethyl -2,2- bis- generations phosphoric acid
Ester 40-60g/L, sodium hypophosphite 40-120g/L, Ce (SO4)25-8g/L, regulation pH value is to be basic in neutrality, and temperature is heated to 40-
60 degrees Celsius；The scolding tin matrix is immersed described solution 1-1.5 hours, to grow the skin covering of the surface in scolding tin matrix surface
Layer.
Preferably, formed during scolding tin matrix and add the percentage by weight of each composition and be：Tin (Sn) 97.95-
98wt%, silver (Ag) 0.3wt%, copper (Cu) 0.7wt%, gallium (Ga) 0.15wt%, indium (In) 0.05wt%, cerium (Ce)
0.8wt%, carbon (C) is less than or equal to 0.05wt%.
Among low temperature resistant oxidation resistant lead-free scolding tin for providing of the present invention and preparation method thereof, by by the content of carbon
Below 0.05wt% (being preferably reduced to be less than or equal to 0.005wt%) is reduced to, the crystal grain of Tin in Tin Solder element can be increased,
So as to increase the heat endurance of scolding tin, and suppress the Sn-Cu alloys invasion and attack that Cu elements are caused, alleviation grows filament；Ga Element
Ga and indium In addition can be anti-oxidant, can also suppress the rapid deterioration occurred under tin (Sn) element low temperature；Cerium Ce or rhenium
Re improves the structural strength of matrix；Aging can be realized by melting again to high temperature fused state under inert environments, help to eliminate internal
Stress, prevention grows the phenomenon of filament；Rapid condensation processing can prevent the fracture phenomena that scolding tin top layer occurs, and avoid easily
Broken phase transformation occurs, and enhances it to the resistance crumbled under low temperature, improves scolding tin heat expansion during extreme changes of temperature cold
The thermal performance of contracting；Surface filming processing is implemented on butt welding tin matrix surface, further pre- anti-oxidation and tin element can go bad, and
And the substituted phosphate of 1- hydroxyethyls -2,2- bis- is to avoiding grown at low temperature filament from having remarkable effect, meanwhile, by controlling film forming
Thickness can keep the welding performance of scolding tin after film forming.
Embodiment
Below by embodiment, technical scheme is described in further detail.
Embodiment one
The formula of following percentage by weight is accounted for according to each composition, scolding tin matrix is prepared：
Metallic tin (Sn) 98wt%, wherein carbon (C) content are not higher than the 0.4wt% of metallic tin gross weight,
Silver (Ag) 0.3wt%,
Copper (Cu) 0.7wt%,
Gallium (Ga) 0.15wt%,
Indium (In) 0.05wt%,
Cerium (Ce) 0.8wt%；
Preparation process is：First, the metallic tin (Sn) in raw material is melted to after 350-360 degrees Celsius, insulated and stirred 20-
30 minutes；Pure oxygen, oxidation removal carbon therein (C) element, control oxygen-supplying amount and time are blown into the tin (Sn) of molten condition, protected
Demonstrate,prove C element content and to be further decreased to 0.05wt% less than or equal to scolding tin matrix gross weight by being not higher than 0.4wt%；Enter one
Step reduction carbon element content, can increase the crystal grain of Tin in Tin Solder element, so as to increase the heat endurance of scolding tin, and press down
The Sn-Cu alloys invasion and attack that Cu elements processed are caused, alleviation grows filament.
According to above percentage by weight, addition silver-colored (Ag), copper (Cu), indium (In), cerium (Ce), and continue 10-20 points of stirring
Clock；It is continuously heating to after 420-430 degrees Celsius, adds gallium (Ga) according to percentage by weight and continue stirring 10-20 minutes, cooling
Sizing turns into scolding tin matrix below to fusing point.
In being formulated more than, the gallium Ga and indium In of addition can be anti-oxidant, can also suppress tin (Sn) element low temperature and issue
Raw rapid deterioration；Cerium Ce can improve the structural strength of matrix.
More than 160 degrees Celsius are warming up to again under the inert atmosphere full of argon gas to the scolding tin matrix, then with 95-
The speed of 100 degree per seconds Celsius is warming up to the scolding tin matrix and melted again, keeps after 3-5 minutes molten conditions, full of argon
The inert atmosphere of gas is solidified as scolding tin matrix again by molten condition with the speed of 10-15 degrees Celsius of cooling per second.Inert environments
Under melt again to high temperature fused state and can realize aging, help to eliminate internal stress, prevention grows the phenomenon of filament；Fast quickly cooling
Solidifying processing can prevent the fracture phenomena that scolding tin top layer occurs, and avoid frangible phase transformation from occurring, and enhance it to being collapsed under low temperature
Bad resistance, improves the thermal performance that scolding tin expands with heat and contract with cold during extreme changes of temperature.
In the superficial film of 7-15 microns of the superficial growth thickness of scolding tin matrix, the film layer coats the surface of scolding tin matrix,
Can be pre- anti-oxidation, and with the addition of avoid tin grown in subzero less than 30 degree low temperature filament-hydroxyethyl -2,2- bis-
Substituted phosphate composition.The specific steps of growing surface film layer include：
Configure following composition and the solution of concentration：
Plus sulfuric acid or NaOH, regulation pH value is 6.5-7.5, basic in neutrality；Temperature is heated to 40-60 degrees Celsius；Keep
The scolding tin matrix is immersed described solution 1-1.5 hours under conditions of said temperature, to grow institute in scolding tin matrix surface
State superficial film.
In above-mentioned solution formula, the substituted phosphate of 1- hydroxyethyls -2,2- bis- through testing repeatedly, it is determined that can be as tin in low temperature
The suppression composition of lower growth filament, sodium hypophosphite is reducing agent, Ce (SO4)2It is antioxidant content, antioxygenic property can be lifted.
Pass through the control to reaction time and temperature and formula concentration, it is ensured that film layer is within above-mentioned thickness range, it is to avoid blocked up
The basic welding performance of the too fast scolding tin for generating film layer and influenceing, such as meltability, mobility and wellability.
Embodiment two
The formula of following percentage by weight is accounted for according to each composition, scolding tin matrix is prepared：
Tin (Sn) 98wt%, wherein carbon (C) content are not higher than the 0.4wt% of metallic tin gross weight；
Silver (Ag) 0.3wt%,
Copper (Cu) 0.7wt%,
Gallium (Ga) 0.15wt%,
Indium (In) 0.05wt%,
Rhenium (Re) 0.8wt%；
Preparation process is：First, the metallic tin (Sn) in raw material is melted to after 350-360 degrees Celsius, insulated and stirred 20-
30 minutes；Pure oxygen, oxidation removal carbon therein (C) element, control oxygen-supplying amount and time are blown into the tin (Sn) of molten condition, protected
Demonstrate,prove C element content and to be further decreased to 0.05wt% less than or equal to scolding tin matrix gross weight by being not higher than 0.4wt%, preferably
For the 0.005wt% less than or equal to scolding tin matrix gross weight；
According to above weight ratio, addition silver-colored (Ag), copper (Cu), indium (In), rhenium (Re), and continue stirring 10-20 minutes；After
Continuous to be warming up to after 420-430 degrees Celsius, addition gallium (Ga) simultaneously continues stirring 10-20 minutes, and being cooled to sizing below fusing point turns into
Scolding tin matrix.
More than 160 degrees Celsius are warming up to again under the inert atmosphere full of argon gas to the scolding tin matrix, then with 95-
The speed of 100 degree per seconds Celsius is warming up to the scolding tin matrix and melted again, keeps after 3-5 minutes molten conditions, full of argon
The inert atmosphere of gas is solidified as scolding tin matrix again by molten condition with the speed of 10-15 degrees Celsius of cooling per second.
In being formulated more than, the gallium Ga and indium In of addition can be anti-oxidant, can also suppress tin (Sn) element low temperature and issue
Raw rapid deterioration；Rhenium Re can improve the structural strength of matrix.
In the superficial film of 7-15 microns of the superficial growth thickness of scolding tin matrix, the film layer coats the surface of scolding tin matrix,
Can be pre- anti-oxidation, and with the addition of avoid tin grown in subzero less than 30 degree low temperature filament-hydroxyethyl -2,2- bis-
Substituted phosphate composition.The specific steps of growing surface film layer include：
First, following composition and the solution of concentration are configured：
SnSO220-30g/L,
The substituted phosphate 40-60g/L of 1- hydroxyethyls -2,2- bis-,
Sodium hypophosphite 40-120g/L,
Hydroquinones 5-8g/L,；
It is basic in neutrality plus sulfuric acid or NaOH regulation pH values are 6.5-7.5；Temperature is heated to 40-60 degrees Celsius；In holding
State under conditions of temperature and to immerse the scolding tin matrix described solution 1-1.5 hour, so as to described in the growth of scolding tin matrix surface
Superficial film.
In above-mentioned solution formula, the substituted phosphate of 1- hydroxyethyls -2,2- bis- through testing repeatedly, it is determined that can be as tin in low temperature
The suppression composition of lower growth filament, sodium hypophosphite is reducing agent, and hydroquinones is the antioxidant content of excellent performance, can be lifted
Antioxygenic property.Pass through the control to reaction time and temperature and formula concentration, it is ensured that film layer be in above-mentioned thickness range with
It is interior, it is to avoid the basic welding performance of the blocked up too fast scolding tin for generating film layer and influenceing, such as meltability, mobility and wellability.
In order to verify effectiveness of the invention, contrast test can be carried out according to the condition described in following table
Above example is merely to illustrate the present invention, and not limitation of the present invention, about the common skill of technical field
Art personnel, without departing from the spirit and scope of the present invention, can also make a variety of changes and modification, therefore all etc.
Same technical scheme falls within scope of the invention, and scope of patent protection of the invention should be defined by the claims.
Claims (12)
1. a kind of low temperature resistant oxidation resistant lead-free scolding tin, including scolding tin matrix and superficial film, it is characterised in that scolding tin matrix into
Point percentage by weight is：
Tin (Sn) 97.95-98wt%, silver (Ag) 0.28-0.32wt%, copper (Cu) 0.68-0.72wt%, gallium (Ga) 0.1-
0.2wt%, indium (In) 0.05-0.1wt%, rhenium (Re) 0.7-0.85wt%, carbon (C) are less than or equal to 0.05wt%；
Also, the scolding tin matrix is to be solidified in an inert atmosphere by molten condition with the speed of 10-15 degrees Celsius of cooling per second
Formed；Scolding tin matrix surface has the superficial film grown according to procedure below：First, the molten of following composition and concentration is configured
Liquid：SnSO220-30g/L, 1- hydroxyethyl -2,2- bis- substituted phosphate 40-60g/L, sodium hypophosphite 40-120g/L, to benzene two
Phenol 5-8g/L, regulation pH value is to be basic in neutrality, and temperature is heated to 40-60 degrees Celsius；The scolding tin matrix is immersed described molten
Liquid 1-1.5 hours, to grow the superficial film in scolding tin matrix surface.
2. Pb-free solder according to claim 1, it is characterised in that the composition by weight percent of scolding tin matrix is：Tin
(Sn) 97.95-98wt%, silver (Ag) 0.3wt%, copper (Cu) 0.7wt%, gallium (Ga) 0.15wt%, indium (In) 0.05wt%, rhenium
(Re) 0.8wt%, carbon (C) is less than or equal to 0.05wt%.
3. Pb-free solder according to claim 1 or 2, it is characterised in that the pH value is adjusted to 6.5-7.5.
4. Pb-free solder according to claim 1 or 2, it is characterised in that the growth thickness of the superficial film is 7-15
Micron.
5. a kind of low temperature resistant oxidation resistant lead-free scolding tin, including scolding tin matrix and superficial film, it is characterised in that scolding tin matrix into
Point percentage by weight is：
Tin (Sn) 97.95-98wt%, silver (Ag) 0.28-0.32wt%, copper (Cu) 0.68-0.72wt%, gallium (Ga) 0.1-
0.2wt%, indium (In) 0.05-0.1wt%, cerium (Ce) 0.7-0.85wt%, carbon (C) are less than or equal to 0.05wt%；
Also, the scolding tin matrix is to be solidified in an inert atmosphere by molten condition with the speed of 10-15 degrees Celsius of cooling per second
Formed；Scolding tin matrix surface has the superficial film grown according to procedure below：First, the molten of following composition and concentration is configured
Liquid：SnSO430-45g/L, 1- hydroxyethyl -2,2- bis- substituted phosphate 40-60g/L, sodium hypophosphite 40-120g/L, Ce (SO4)25-8g/L, regulation pH value is to be basic in neutrality, and temperature is heated to 40-60 degrees Celsius；The scolding tin matrix is immersed into the solution
1-1.5 hours, to grow the superficial film in scolding tin matrix surface.
6. Pb-free solder according to claim 5, it is characterised in that the composition by weight percent of scolding tin matrix is：Tin
(Sn) 97.95-98wt%, silver (Ag) 0.3wt%, copper (Cu) 0.7wt%, gallium (Ga) 0.15wt%, indium (In) 0.05wt%, cerium
(Ce) 0.8wt%, carbon (C) is less than or equal to 0.05wt%.
7. the Pb-free solder according to claim 5 or 6, it is characterised in that the pH value is adjusted to 6.5-7.5.
8. the Pb-free solder according to claim 5 or 6, it is characterised in that the growth thickness of the superficial film is 7-15
Micron.
9. a kind of preparation method of low temperature resistant oxidation resistant lead-free scolding tin, it is characterised in that comprise the following steps：
Step 1, the metallic tin (Sn) for taking phosphorus content to be not higher than 0.4wt% is raw material, and metallic tin (Sn) is melted into 350-360 and taken the photograph
After family name's degree, insulated and stirred 20-30 minutes；Pure oxygen, oxidation removal carbon therein (C) element are blown into the tin (Sn) of molten condition；
Step 2, to metallic tin (Sn) addition silver-colored (Ag) of the molten condition after oxidation, copper (Cu), indium (In), rhenium (Re), and after
Continuous stirring 10-20 minutes；It is continuously heating to after 420-430 degrees Celsius, addition gallium (Ga) simultaneously continues stirring 10-20 minutes, cooling
Sizing turns into scolding tin matrix below to fusing point；Wherein, formed during scolding tin matrix and add the percentage by weight of each composition and be：
Tin (Sn) 97.95-98wt%, silver (Ag) 0.28-0.32wt%, copper (Cu) 0.68-0.72wt%, gallium (Ga) 0.1-
0.2wt%, indium (In) 0.05-0.1wt%, rhenium (Re) 0.7-0.85wt%, carbon (C) are less than or equal to 0.05wt%；
Step 3, more than 160 degrees Celsius are warming up to again under the inert atmosphere full of argon gas to the scolding tin matrix, then with
The speed of 95-100 degree per seconds Celsius is warming up to the scolding tin matrix and melted again, keep 3-5 minutes molten conditions after, full of
The inert atmosphere of argon gas is solidified as scolding tin matrix again by molten condition with the speed of 10-15 degrees Celsius of cooling per second；
Step 4, following composition and the solution of concentration are configured：SnSO2The substituted phosphate 40- of 20-30g/L, 1- hydroxyethyl -2,2- bis-
60g/L, sodium hypophosphite 40-120g/L, hydroquinones 5-8g/L, regulation pH value is to be basic in neutrality, and temperature is heated to 40-60 and taken the photograph
Family name's degree；The scolding tin matrix is immersed described solution 1-1.5 hours, so as in scolding tin matrix surface growing surface film layer.
10. the preparation method of Pb-free solder according to claim 9, it is characterised in that add during formation scolding tin matrix
Plus the percentage by weight of each composition is：Tin (Sn) 97.95-98wt%, silver (Ag) 0.3wt%, copper (Cu) 0.7wt%, gallium (Ga)
0.15wt%, indium (In) 0.05wt%, rhenium (Re) 0.8wt%, carbon (C) are less than or equal to 0.05wt%.
11. a kind of preparation method of low temperature resistant oxidation resistant lead-free scolding tin, it is characterised in that comprise the following steps：
Step 1, the metallic tin (Sn) for taking phosphorus content to be not higher than 0.4wt% is raw material, and metallic tin (Sn) is melted into 350-360 and taken the photograph
After family name's degree, insulated and stirred 20-30 minutes；Pure oxygen, oxidation removal carbon therein (C) element are blown into the tin (Sn) of molten condition；
Step 2, to metallic tin (Sn) addition silver-colored (Ag) of the molten condition after oxidation, copper (Cu), indium (In), cerium (Ce), and after
Continuous stirring 10-20 minutes；It is continuously heating to after 420-430 degrees Celsius, addition gallium (Ga) simultaneously continues stirring 10-20 minutes, cooling
Sizing turns into scolding tin matrix below to fusing point；Wherein, formed during scolding tin matrix and add the percentage by weight of each composition and be：
Tin (Sn) 97.95-98wt%, silver (Ag) 0.28-0.32wt%, copper (Cu) 0.68-0.72wt%, gallium (Ga) 0.1-
0.2wt%, indium (In) 0.05-0.1wt%, cerium (Ce) 0.7-0.85wt%, carbon (C) are less than or equal to 0.05wt%；
Step 3, more than 160 degrees Celsius are warming up to again under the inert atmosphere full of argon gas to the scolding tin matrix, then with
The speed of 95-100 degree per seconds Celsius is warming up to the scolding tin matrix and melted again, keep 3-5 minutes molten conditions after, full of
The inert atmosphere of argon gas is solidified as scolding tin matrix again by molten condition with the speed of 10-15 degrees Celsius of cooling per second；
Step 4, following composition and the solution of concentration are configured：SnSO4The substituted phosphate 40- of 30-45g/L, 1- hydroxyethyl -2,2- bis-
60g/L, sodium hypophosphite 40-120g/L, Ce (SO4)25-8g/L, regulation pH value is to be basic in neutrality, and temperature is heated to 40-60 and taken the photograph
Family name's degree；The scolding tin matrix is immersed described solution 1-1.5 hours, so as in scolding tin matrix surface growing surface film layer.
12. the preparation method of Pb-free solder according to claim 11, it is characterised in that add during formation scolding tin matrix
Plus the percentage by weight of each composition is：Tin (Sn) 97.95-98wt%, silver (Ag) 0.3wt%, copper (Cu) 0.7wt%, gallium (Ga)
0.15wt%, indium (In) 0.05wt%, cerium (Ce) 0.8wt%, carbon (C) are less than or equal to 0.05wt%.
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| CN112171104A (en) * | 2020-09-11 | 2021-01-05 | 江苏佳华金属线有限公司 | Preparation method of antioxidant soldering tin for tinned copper wire |
| CN112658527A (en) * | 2020-12-15 | 2021-04-16 | 苏州雷盾新材料科技有限公司 | Leadless low-temperature soldering tin |
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| CN1475327A (en) * | 2003-06-28 | 2004-02-18 | 亚通电子有限公司 | Antioxidation leadless welding material |
| CN1570166A (en) * | 2004-05-09 | 2005-01-26 | 邓和升 | Lead free solder alloy and its preparation method |
| CN1583349A (en) * | 2004-05-28 | 2005-02-23 | 四川省有色冶金研究院 | High performance leadless tin-copper solder for electronic elements |
| CN1678769A (en) * | 2002-10-18 | 2005-10-05 | 株式会社日矿材料 | Surface treatment agent for Sn alloy and method of surface treatment |
| CN1799759A (en) * | 2006-01-04 | 2006-07-12 | 东莞市千岛金属锡品有限公司 | Lead-free solder and its preparation method |
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| CN1678769A (en) * | 2002-10-18 | 2005-10-05 | 株式会社日矿材料 | Surface treatment agent for Sn alloy and method of surface treatment |
| CN1823181A (en) * | 2003-05-16 | 2006-08-23 | 索尼株式会社 | Surface treating agent for tin or tin alloy material |
| CN1475327A (en) * | 2003-06-28 | 2004-02-18 | 亚通电子有限公司 | Antioxidation leadless welding material |
| CN1570166A (en) * | 2004-05-09 | 2005-01-26 | 邓和升 | Lead free solder alloy and its preparation method |
| CN1583349A (en) * | 2004-05-28 | 2005-02-23 | 四川省有色冶金研究院 | High performance leadless tin-copper solder for electronic elements |
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